Reforming with a non-noble-metal-mordenite catalyst

ABSTRACT

THE CATALYST COMPRISES A HYDROGENATION COMPONENT COMPRISING A MEMBER SELECTED FROM THE GROUP CONSISTING OF A METAL OF GROUP VI-A, COMPOUNDS OF A METAL OF GROUP VI-A, AND MIXTURES THEREOF SUPPORTED ON A CO-CATALYTIC SOLID SUPPORT COMPRISING MORDENITE AND A POROUS REFRACTORY INORGANIC OXIDE. THE HYDROGENATION COMPONENT MAY BE CHARACTERIZED FURTHER BY A MEMBER SELECTED FROM THE GROUP CONSISTING OF RHENIUM, COMPOUNDS OF RHENIUM, A NON-NOBLE METAL OF GROUP VIII, COMPOUNDS OF A NON-NOBLE METAL OF GROUP VIII, AND MIXTURES THEREOF. THE PREFERRED GROUP VI-A METAL IS MOLYBDENUM. A REFORMING PROCESS COMPRISES CONTACTING A PETROLEUM HYDROCARBON STREAM IN A REFORMING ZONE UNDER REFORMING CONDITIONS AND IN THE PRESENCE OF HYDROGEN WITH THE ABOVE CATALYST. IN ONE EMBODIMENT. THE PROCESS COMPRISES CONTACTING A PARTIALLY-REFORMED HYDROCARBON STREAM IN A REFORMING ZONE UNDER REFORMING CONDITIONS AND IN THE PRESENCE OF HYDROGEN WITH THE ABOVE CATALYST. IN ANOTHER EMBODIEMENT, THE PROCESS COMPRISES CONTACTING THE PETROLEUM HYDROCARBON STREAM IN A FIRST REFORMING ZONE UNDER REFORMING CONDITIONS AND IN THE PRESENCE OF HYDROGEN WITH A CATALYST COMPRISING A PLATINUM GROUP METAL AND A HALIDE ON ALUMINA TO PRODCE A FIRST REFORMATE AND SUBSEQUENTLY CONTACTING THE FIRST REFORMATE IN A SECOND REFORMING ZONE UNDER REFORMING CONDITIONS AND IN THE PRESENCE OF HYDROGEN WITH THE AVOVE CATALYST.

Mllch 19, 1974 R. J. BERTOLACINI Erm. 3,798,154

REFORMING WITH A NON-NOBLE-METALMORDENITE CATALYST Filed March l, 1972 United States Patent O U.S. Cl. 208-65 24 Claims ABSTRACT OF THE DISCLOSURE The catalyst comprises a hydrogenation component comprising a member selected from the group consisting of a metal of Group VI-A, compounds of a metal of Group VI-A, and mixtures thereof supported on a co-catalytic solid support comprising mordenite and a porous refractory inorganic oxide. The hydrogenation component may be characterized further by a member selected from the group consisting of rhenium, compounds of rhenium, a non-noble metal of Group VIII, compounds of a non-noble metal of Group VIII, and mixtures thereof. The preferred Group VI-A metal is molybdenum.

A reforming process comprises contacting a petroleum hydrocarbon stream in a reforming zone under reforming conditions and in the presence of hydrogen with the above catalyst. In one embodiment, the process comprises contacting a partially-reformed hydrocarbon stream in a reforming zone under reforming conditions and in the presence of hydrogen with the above catalyst. In another embodiment, the process comprises contacting the petroleum hydrocarbon stream in a rst reforming zone under reforming conditions and in the presence of hydrogen With a catalyst comprising a platinum group metal and a halide on alumina to produce a rst reformate and subsequently contacting the first reformate in a second reforming zone under reforming conditions and in the presence of hydrogen with the above catalyst.

This is a division of application Ser. No. 115,6l3, filed Feb. 16, 1971, now abandoned.

BACKGROUND OF THE INVENTION The reforming of petroleum hydrocarbons streams is one of the important petroleum refining processes that may be employed to provide high-octane-number hydrocarbon blending components for gasoline. In the typical reforming process, the reactions comprise dehydrogenation reactions, isomerization reactions, and hydrocracking reactions. The dehydrogenation reactions include the dehydrogenation of cyclohexanes to aromatics, the dehydroisomerization of alkylcyclopentanes to aromatics, the dehydrogenation of paraflins to olens, and the dehydrocyclization of parafns and olens to aromatics, The isomerization reactions include isomerization of n-parains to isoparaflins, the hydroisomerization of olelins to isoparaffins, the isomerization of alkylcyclopentanes to cyclohexanes, and the isomerization of substituted aromatics. The hydrocracking reactions include hydrocracking of parafiins and hydrodesulfurization. Adequate discussion of the reactions occurring in a reforming reaction zone are presented in Catalysis, vol. VI, P. H. Emmett, editor, Reinhold Publishing Corporation, `1958, pages 497-498, and Petroleum Processing, R. J. Hengstebeck, McGraw-Hill Book Company, Inc., 1959, pages 179-184.

It is Well known by those skilled in the art that several catalysts are capable of reforming petroleum naphthas and hydrocarbons that boil in the gasoline boiling range. Although reforming may be carried out through the use of molybdena-on-alumina catalysts, chromium-oxides-on-alumina catalysts, platinum-halogen-on-alumina catalysts, and platinum-aluminosilicate-material-alumina catalysts, the catalysts employing platinum as a hydrogenation component are generally employed today in the reforming processes of the petroleum industry.

It has been found that improved reforming may be eifected by the use of another catalytic composition that does not contain a noble metal of Group VI-II of the Periodic Table of Elements. This catalyst is particularly suited for use either as the catalyst in a reforming system that is employed to convert mildly-reformed or partiallyreformed naphthas and hydrocarbon streams or as the second or last catalyst in a multiple-catalyst reforming system.

Embodiments of the reforming process employing this non-noble-metal catalyst, the process of the present invention, provide high-octane-number blending material for unleaded and/or low-lead motor fuels.

SUMMARY OF THE INVENTION Broadly, according to the present invention, there is provided a process for reforming a petroleum hydrocarbon stream, which process comprises contacting said hydrocarbon stream in a reforming zone under reforming conditions and in the presence of hydrogen with a nonnoble-metal catalytic composition. This non-noble-metal catalytic composition, hereinafter referred to as the nonnoble-metal catalyst, is a catalyst comprising a hydrogenation component comprising a member selected from the group consisting of a metal of Group VI-A of the Periodic Table of Elements, compounds of a metal of Group VI-A, and mixture thereof supported on a co-catalytic solid support comprising mordenite and a porous refractory inorganic oxide. The preferred Group VI-A metal is molybdenum. The hydrogenation component may be characterized further by a member selected from the group consisting of rhenium, compounds of rhenium, a nonnoble metal of Group VIII of the Periodic Table of Elements, compounds of a non-noble metal of Group VIII, and mixtures thereof. The preferred refractory inorganic oxide is a catalytically active alumina.

In one embodiment of the process of the present invention, there is provided a process for reforming a partiallyreformed hydrocarbon stream. This process comprises contacting the partially-reformed hydrocarbon stream in a reforming zone under reforming conditions and in the presence of hydrogen with the non-noble-metal catalyst.

In another embodiment of the process of the present invention, there is provided a process for reforming a petroleum hydrocarbon stream, which process comprises contacting said hydrocarbon stream in a first reforming zone under reforming conditions and in the presence of hydrogen with a catalyst comprising a platinum group metal and a halide on a catalytically active alumina to produce a first reformate and subsequently contacting said rst reformate in a second reforming zone under reforming conditions and in the presence of hydrogen with the non-noble-metal catalyst.

Accordingly, the process may employ the non-noblemetal catalyst of the present invention either as the sole catalyst in the reforming process, or, preferably, as the final catalyst in a multiple-catalyst reforming system. Preferredly, the process employs the catalyst of the invention in the last reactor, or tail reactor, of a multiple-reactor reforming system. The selection of the particular embodiment of the process of the present invention Will be dictated by the feedstock to be reformed. If the hydrocarbon stream has already been partially reformed, the embodiment of the process employing the non-noble-metal catalyst as the sole catalyst is suitable.

3 BRIEF DESCRIPTION OF THE DRAWING The attached figure presents, a simpliiied schematic flow diagram of a preferred embodiment of the process of the present invention wherein the non-noble-metal catalytic composition of the present invention is employed in the last reactor, or tail reactor, of a multiple-reactor reforming system.

DESCRIPTION AND PREFERRED EMBODIMENTS The highly mechanized society of today requires an increasing demand for very-high-octane-number motor fuels. The process of this invention is especially advantageous for the production of high-octane-number blending components for motor fuels by means of the reforming of petroleum naphthas and petroleum hydrocarbon streams boiling in the gasoline boiling range. It may be employed suitably to produce high-octane-number blending components for unleaded and/ or low-lead motor fuels.

The embodiments of the process of the present invention may be used to reform a feedstock which is a member selected from the group consisting of a virgin naphtha, a cracked naphtha, a hydrocarbon fraction boiling in the gasoline boiling range, mixture thereof, and partially-reformed naphthas and other hydrocarbon streams. A naphtha will exhibit a boiling range of about 70 to about 500 F., preferably, about 180 to about 400 F. The gasoline boiling range comprises temperatures of about 120 to about 420 F., preferably, about 140 to about 380 F. The partially-reformed hydrocarbon streams will exhibit an unleaded research octane number within the range of about 75 to about 95. Since many of the above feedstocks may contain appreciable amounts of nitrogen and sulfur compounds, which are deleterious to the lrst catalyst of that embodiment of the present invention which employs a multiple-catalyst reforming system, it is preferred that the feedstock in this case be subjected to a suitable hydrodesulfurization and/ or hydrodenitrogenation treatment, such as hydroiining, prior to use in the embodiment of the process of the present invention in order to reduce both the nitrogen and sulfur levels to tolerable limits.

The process of this invention is capable of upgrading a 50% naphthenic naphtha having a research octane number as low as 40 into a C5+gasoline having a research octane number in excess of 100 at a yield of 65 to 90%. Higher C5+octane reformates may be produced at slightly reduced yields as the octane value is increased.

The non-noble-metal catalytic composition of the present invention may be employed for the conversion of various petroleum hydrocarbon streams. In particular, it is a suitable catalyst for the reforming of petroleum naphthas and petroleum hydrocarbon streams boiling in the gasoline boiling range. This catalytic composition comprises a hydrogenation component comprising a member selected from the group consisting of a metal of Group VI-A of the Periodic Table of Elements, compounds of a metal of Group VI-A, and mixtures thereof supported on a co-catalytic solid support comprising mordenite and a porous refractory inorganic oxide.

The hydrogenation component comprises a metal of Group VI-A of the Periodic Table of Elements and/or its compounds. In particular, the compounds may be the oxides and/or suldes of the Group VI-A metal. Moreover, this hydrogenation component may be characterized further by a member selected from the group consisting of rhenium, a non-noble metal of Group VIII of the Periodic Table of Elements, compounds of rhenium, compounds of the non-noble metal of Group VIII, and mixtures thereof. The metal of Group VI-A may be molybdenum, chromium, or tungsten. Molybdenum is the preferred group VI-A metal. When molybdenum is the metal of Group VI-A, it is present in an amount within the range of about 2 weight percent to about 20 weight perment, calculated as M003. Preferably, molybdenum is present in an amount within the range of about 5 weight percent to about 15 weight percent, calculated as M003.

Rhenium and the non-noble metal of Group VIII of the Periodic Table may be present as the elements, as cornpounds such as oxides and sulfides, and as mixtures thereof. The preferred non-noble metals of Group VIII are cobalt and nickel. Rhenium may be persent in a maximum amount of about 4 Weight percent, based on the weight of the catalyst. The non-noble metals of Group VIII may be present in an amount within the range of about 0.1 weight percent to about 5 weight percent, calculated as their oxides.

The co-catalytic solid support of the non-noble-metal catalytic composition of the present invention comprises a mordcnite-type-aluminosilicate material and a porous refractory inorganic oxide. Suitably, the mordenite is suspended in and distributed throughout a matrix of the porous refractory inorganic oxide.

Preferably, the mordenite-type aluminosilicate material has been cation-exchanged with a member selected from the group consisting of an alkaline earth metal, a rare earth metal, hydrogen, and a hydrogen precursor to red-uce the sodium content to a level that is less than l weight percent, calculated as the metal. The mordenitetype aluminosilicate material may be persent in the cocatalytic solid support in an amount within the range of about 1 weight percent to about 50 weight percent, based on the weight of said support.

A preferred mordenite-type alminosilicate material is the synthetic Zeolon manufactured by the Norton Chemical Company. Zeolon-H is the hydrogen form of this synthetic mordenite. Mordenite is characterized by its high silica-to-alumina ratio and its crystal structure. The mordenite may have a silica-to-alumina ratio within the range of about 6 to about 100. The composition of mordenite is given in Kirk-Othmer, Encyclopedia of Chemical Technology, rst edition, volume l2, page 297 (1954), as (Ca, Na2)Al2Si9O22-6H2O. The proposed structure is one in which the basic building block is a tetrahedron consisting of 1 silicon or aluminum atom surrounded by four oxygen atoms. The crystal structure is made up of 4- or S-membered rings of these tetrahedra. These 4- and S-rnembered rings are believed to give the structure its stability. The chains are linked together to form a network having a system of large parallel channels interconnected by small cross channels. Rings of l2 tetrahedra form the large channels. Other synthetic zeolites also have such lZ-membered rings, but they have interconnected cages, whereas the mordenite has parallel channels of uniform diameter. For example, synthetic faujasite, which has the formula Na3Al3Si4O14, is characterized by a 3-dimension array of pores which consist of 12-13 angstrom (A.) cages interconnected through 8-9 A. windows.

The mordenite in the catalytic composition of the present invention may be in the unexchanged cation form containing exchangeable sodium and/or calcium ions, or other alkali metal or alkaline earth metal ions. Preferably, the alkali metal cations, such as sodium ions, may be replaced or cation-exchanged with a member selected from the group consisting of an alkaline earth metal, a rare earth metal, hydrogen, and a hydrogen precursor to provide an alkali metal content in the mordenite that is less than 1 weight percent, calculated as the metal. Ammonium ions comprise a hydrogen precursor and may be employed to lcation-exchange the a'lkali metal of the mordenite. Heat is employed to drive olf ammonia leaving the mordenite in the hydrogen form. Mordenite differs from other aluminosilicates in that substantially all the exchangeable metal cations may be replaced with hydrogen ions without causing destruction of the characteristic crystal structure of the mordenite.

The porous refractory inorganic oxide that is employed in the non-noble-metal catalytic composition of the present invention may be a catalytically active alumina, silicaalumina, silica-magnesia, titania-alumina, zinc-oxidealumina, and the like. Catalytically active alumina, such as gamma-alumina and eta-alumina, is the preferred refractory inorganic oxide. Such alumina should have a pore diameter of about 70 angstroms to about 200 angstroms and a surface area of at least 150 square meters per gram. Suitably, the surface area should be within the range of about 200 square meters per gram to about 500 square meters per gram.

The non-noble-metal catalytic composition of the present invention may be prepared in various ways. For example, finely divided mordenite-type aluminosilicate material may be stirred into a sol or gel of the refractory inorganic oxide and a soluble compound of the hydrogenation metal or soluble compounds of the hydrogenation metals added to the sol or gel, followed by the cogelling of' the sol or gel mixture by the addition of dilute ammonia. The resulting cogelled material is then dried and calcined. In another method of preparation, the finely divided mordenite is mixed into a sol or gel of the refractory inorganic oxide, the sol or gel mixture is cogelled by the addition of dilute ammonia and the resulting gel is subsequently dried, pelleted, calcined, cooled, and impregnated with a solution of the hydrogenation metal or solutions of the hydrogenation metals. As an alternate method of preparation, a hydrogel of the refractory inorganic oxide is blended with finely divided aluminosilicate material, and a solution of a soluble compound of the hydrogenation metal or solutions of soluble compounds of the hydrgenation metals are added to this blend, and the resulting mixture is thoroughly blended. The blended mixture is then dried, pelleted, and calcined. Suitable drying conditions for use in the above described metal manufacturing methods comprise a temperature in the range of about 200 F. to about 400 F. and a drying time of about 5 to 30 hours. Suitable calcination conditions comprise a temperature in the range of about 900 to 1,400 F. and a calcination time of about 2 to about 20 hours. Preferred drying and calcination conditions are a temperature of about 250 F. for about 16 hours and a temperature of about 1,000 F. for about 6 hours, respectively.

The non-noble-metal catalyst of the present invention is suitable for the conversion of petroleum hydrocarbon streams. In particular, it is employed for the reforming of petroleum hydrocarbon naphthas and those petroleum hydrocarbon streams boiling in the gasoline boiling range. This non-noble-metal catalyst is effective for converting the heavy paraflins remaining in a reformate, therefore, a preferred embodiment of the process of the present invention is a process which employs a catalyst comprising a platinum group metal and a halide on alumina in a first reforming zone and the catalytic composition of the present invention in a second reforming zone. Still more particularly, the catalyst comprising a platinum group metal and a halide on alumina is employed in all of the reactors except the tail reactor and the catalytic composition of the present invention is employed in the tail reactor. For selected 'conditions and selected feedstocks, it is contemplated that the first reforming zone could constitute two or more reactors and the second reforming zone could constitute at least one reactor. In an alternative embodiment of the process of the present invention, the reforming system could comprise one or more reactors containing the nonnoble-metal catalyst of the present invention and making up a sole reaction zone. To this latter embodiment, a partially-reformed napht-ha would be the ideal feedstock.

According to the present invention, there is provided a process for reforming a petroleum hydrocarbon stream, which process comprises contacting said hydrocarbon stream in a reforming zone under reforming conditions and in the presence of hydrogen with the non-noble-metal catalyst as described hereinabove. In one embodiment, the process comprises contacting a partially-reformed hydrocarbon stream in a reforming zone under reforming conditions and in the presence of hydrogen with the non-noblemetal catalyst. In another embodiment of the process of the present invention, the process comprises contacting a petroleum hydrocarbon stream in a first reforming zone under reforming conditions and in the presence of hydrogen with a catalyst comprising a platinum group metal and a halide on alumina to produce a first reformate and subsequently contacting said first reformate in a second reforming zone under reforming conditions and in the presence of hydrogen with the non-noble-metal catalyst. This latter embodiment is a process wherein the first reforming zone comprises two or more reactors and the second reforming zone comprises at least one reactor. The platinum group metals include platinum, iridium, osmium, palladium, rhodium, and ruthenium. Platinum is the preferred platinum group metal. Chloride and fluoride are the preferred halides.

Typical operating conditions of this reforming process comprise an average catalyst temperature of about 850 F. to about 1,050 F., a pressure of about 50 p.s.i.g. to about 1,000 p.s.i.g., a weight hourly space velocity (WHSV) of about 0.5 to about l0 weight units of hydrocarbons per hour per Weight unit of catalyst, and a hydrogen addition rate of about 1,500 standard cubic feet per barrel (s.c.f.b.) to about 15,000 s.c.f.b. Preferred reforming conditions comprise an average catalyst temperature of about 875 F. to about 1,000 F., a pressure of about 50 p.s.i.g. to about 450 p.s.i.g., a WHSV of about 0.9 to about 4 weight units of hydrocarbon per hour per weight unit of catalyst, and a hydrogen addition rate of about 4,000 s.c.f.b. to about 10,000 s.c.f.b. These operating conditions are appropriate for each reforming zone of the multiple-zone embodiment of the process of the present invention.

The process of the present invention can be carried out in any of the conventional types of equipment known to the art. One may, for example, employ catalysts in the form of pills, pellets, granules, broken fragments, or various special shapes, disposed as one or more fixed beds within one or more reaction zones, and the charging stock may be passed therethrough in the liquid, vapor, or mixed phase, and in either upward or downward flow. Alternatively, the catalysts may be in a suitable form for use in moving beds, in which the charging stock and catalyst are preferably passed in countercurrent flow; or in uidized-solid processes, in which the charging stock is passed upward through a turbulent bed of finely divided catalyst; or in the suspensoid process, in which the catalyst is slurried in the charging stock and the resulting mixture is conveyed into the reaction zone. A fixed-bed reforming process is exemplified by Ultraforming (Petroleum Engineer, vol. XXVI, No. 4, April 1954, at page C-35). In a six-reactor unit with the five fixed-bed reactors on oil and one fixed-bed reactor under regeneration, it is convenient to employ the non-noble-metal-mordenite-containing catalyst in the last reactor and a mixture (or layers) of the two catalysts in the swing reactor. The reaction products from any of the foregoing processes are separated from the catalyst and fractionated to recover the various components thereof. The hydrogen and unconverted materials are recycled as desired, the excess hydrogen produced in the reformer conveniently being utilized in the hydroesulfurization of the feed.

Unwanted products in the reforming of petroleum hydrocarbon streams are light hydrocarbon gases and coke. Such products and other compounds, such as polynuclear aromatics and heavy hydrocarbons, result in coke. As the operation progresses, a substantial amount of coke accumulates on the surface of each of the catalysts resulting in an increasingly rapid rate of catalyst deactivation. Consequently, the coke must be removed periodically from the surface. Such coke removal may be accomplished through a coke-burn treatment wherein the coked catalyst is contacted with an oxide-containing gas at selected temperatures. Typically, the gas will contain oxygen within the range of about 1.0 volume percent to about 21 volume percent. The concentration of oxygen in the gas should be maintained at a level which will not result in the production of temperatures that will be in excess of 1,100 F., preferably, in excess of 1,050 F.

The non-noble-metal catalytic composition of the present invention is capable of being regenerated and is capable of withstanding the conditions employed in the regeneration treatment. If the catalyst is employed in au embodiment of the process which also employs one or more other reforming catalysts, such other catalysts should be capable of being regenerated.

A preferred embodiment of the process of the present invention is depicted in the accompanying ligure. This ligure is a simplified schematic ow diagram of the preferred embodiment. It does not include certain auxiliary equipment, such as heat exchangers, valves, pumps, compressors, and associated equipment, which would be needed in various places along the ilow path of the process in addition to the pump and compressor that are depicted in the drawing. Such additional auxiliary equipment and its location requirements would be quickly recognized by one having ordinary skill in the art. Therefore, such equipment is not shown in the ligure.

In the embodiment represented in the ligure, a naphtha heart cut, having a boiling range of about 160 F. to about 400 F., preferably, about 180 F. to about 380 F., is obtained from source 10. This feedstock is passed through line 11 into pump 12, which pumps the hydrocarbons through line 13. Hydrogen-containing recycle gas is introduced into line 13 via line 14 to be mixed with the hydrocarbons in line 13. The resulting hydrogen-hydrocarbon mixture passes through line 13, furnace 15, and line 16 into the top of reactor 17. The material is introduced into reactor 17 at a temperature of about 940 F. The outlet temperature of reactor 17 is approximately 760 F. and the pressure in reactor 17 is within the range of about 80 p.s.i.g. to about 90 p.s.i.g.

The eiliuent from reactor 17 passes through line 18, furnace 19, and line 20 into the top of reactor 21. Sufiicient heat is introduced into this hydrogen-hydrocarbon stream by furnace 19 so that the temperature at the inlet of reactor 21 is approximately 960 F. The outlet temperature of reactor 21 is approximately 855 F. and the pressure in reactor 21 is within the range of about 70 p.s.i.g. to about 80 p.s.ig.

The eiliuent from reactor 21 passes through line 22, furnace 23, and line 24 into the top of reactor 25. This eiuent is heated in furnace 23 so that the inlet temperature of reactor 25 is approximately 960 F. The outlet temperature of reactor 25 is approximately 940 F. and the pressure in reactor 25 is within the range of about 60 p.s.i.g. to about 70 p.s.i.g.

The eluent from reactor 25 passes through line 26, furnace 27, and line 28 into the top of reactor 29. This hydrocarbon eiuent is heated in furnace 27 so that the inlet temperature of reactor 29 is about 980 F. The outlet temperature of reactor 29 is about 960 F. and the pressure in reactor 29 is within the range of about 50 p.s.i.g. to about 60 p.si.g.

Reactors 17, 21, and 25 all contain a catalyst comprising platinum and chloride on a support of catalytically active alumina. The catalyst may be promoted by a small amount of rhenium. In general, the catalyst contains 0.1 to about 2 weight percent platinum and 0.1 to 5 weight percent chloride, preferably, 0.4 to l weight percent chloride. The fourth reactor, or tail reactor, in the system contains an embodiment of the non-noble-metal catalytic composition of the present invention. This embodiment of the catalytic composition comprises about l weight percent M003 and 2 weight percent Zeolon-H, dispersed in and suspended throughout a matrix of catalytically active alumina.

Not shown in the ligure is a fifth reactor, which reactor contains a mixture or layers of the two catalysts. This additional reactor is employed as a swing reactor for each of the four reactors in this system when the catalyst in a particular reactor has become deactivated and must be regenerated. The reactor containing this deactivated catalyst is removed from the system and is replaced by the swing reactor in order that the reforming system may be operated continuously, even though the deactivated catalyst has been removed from the system and is being regenerated.

The hydrogen-hydrocarbon ratio and the WHSV employed in the various reactors fall within the respective ranges of values as expressed hereinabove.

The eliluent from reactor 29 passes through line 30, water cooler 31, and line 32 into gas-liquid separator 33. Gas-liquid separator 33 is operated at a pressure of about 15 p.s.i.g. to about 30 p.s.i.g. and at temperatures of about 100 F. Liquid product is removed from separator 33 through line 34 to be sent to a suitable product recovery system from which a high-octane-number product is obtained. Gaseous material is removed from separator 33 through line 35. A portion of this gas is removed from the system through line 36' to be used at other relinery units. The remainder of the hydrogen-hydrocarbon gas in line 35 is compressed by compressor 37 to be sent through lines 38 and 14 as hydrogen-hydrocarbon recycle gas. When necessary, make-up hydrogen gas may be introduced into the system from source 39 via line 40.

The following examples are presented herein to facilitate the understanding of the present invention. These examples are presented for the purpose of illustration only and are not intended to limit the scope of the present invention.

EXAMPLE I An embodiment of the non-noble-metal catalyst of the present invention was to be compared with two other reforming catalysts. A description of each of these catalysts is presented in this example.

A catalyst comprising the oxides of molybdenum on a catalytically active alumina was prepared in the laboratory. An ammonium molybdate solution was prepared by dissolving 24.3 grams of ammonium heptamolybdate, (NH4) 6Mo7O244H2O, in 200 m1. of warm distilled water (about 160 F.). This solution was then thoroughly blended with an 80G-gram portion of an alumina gel obtained from the Filtrol Corporation. This alumina gel contained 22.5 weight percent alumina. The blend was dried in air for 3 hours at a temperature of about 250 F. and calcined in air for 1 hour at 1,000 F. The air -ow rate during the drying and calcination operations for this and subsequent laboratory catalyst preparations were maintained at about 1.5 cubic feet per hour. The

` calcined material was subsequently pelleted into lA- x 1A- inch pellets. About 4% sterotex was employed for the pelleting. The pellets were then calcined for 3 hours in air at a temperature of 1,000 F. This catalyst was prepared to contain 10 weight percent M003 and is identified hereinafter as Catalyst A.

A catalyst comprising the oxides of molybdenum on a support of mordenite aluminosilicate material and alumina was prepared. An ammonium molybdate solution was prepared by dissolving 24.3 grams of iammonium heptamolybdate in 300 ml. of Iwarm distilled Water (about F). This solution of and a 4-gram portion of linely divided Zeolon-H were thoroughly blended with a 782- gram portion of an alumina gel obtained from the Filtrol Corporation. This alumina gel contained 22.5 weight percent alumina. The resulting blend was dried in air for 3 hours at a temperature of about 250 F. and calcined for 1 hour in air at 1,000 F. The dried material was then pelleted into 1%1- x 1Ai-iuch pellets. About 4% sterotex was employed in this pelleting operation. The pellets were calcined subsequently in air for 3 hours at 1,000 F. This catalyst was prepa-red to contain 10 weight percent M003 and 2 weight percent Zeolon-H and is hereinafter identied as Catalyst B. Zeolon-H is the hydrogen form of synthetic mordenite aluminosilcate material manufactured by the Norton Chemical Company.

A commercially prepared catalyst comprising platinum and chloride on alumina was obtained from the American Cyanamid Company. This catalyst contained 0.77 Weight percent platinum and 0.88 weight percent chloride on a gamma-alumina and was obtained in the form of j,4G-inch extrudates. This catalyst is identified hereinafter as Catalyst C.

EXAMPLE II The above catalysts were tested individually in a microow test unit. In this unit, a mixture of preheated oil and hydrogen was passed over a small sample of the catalyst being studied. Hydrogen was obtained from a cylinder and the hydrocarbon stream was pumped into the unit by a positive-displacement pump. The reactor had an internal diameter of 0.622 inch and was inches long. The catalyst bed was supported on a layer comprising 3 cc. of glass beads. The olf-gas was continuously vented and the liquid produtc was collected in either a product receiver or a slop receiver. The reactor was immersed in a heat bath of Du Pont Hytec. Temperatures in the reactor were determined by employing a manually-operatedco-axial thermocouple. The reactor was operated under essentially isothermal conditions. For the purpose of obtaining an octane number, a liquid sample was collected for a period of about 18 hours. For weight balance information, a 1 hour accumulated liquid sample was obtained. Analyses were obtained by means of gas-chromatographic techniques. Prior to being charged into the reactor, each catalyst was ground to a 20-40 mesh material (U.S. Sieve Series).

The feedstock employed in the tests described in this example is a mildly-reformed mid-continent naphtha possessing the properties listed in Table I.

TABLE I Feedstoc-k properties Each of the catalysts of Example I was tested in the micro-unit with the above feedstock. The average catalyst temperature employed was the kinetic average temperature of the catalyst bed. Each of the catalyst beds occupied from about 6% to about 8 inches of reactor length. The results of the tests are presented in Table II.

Each of the tests simulated a reforming system in which a naphtha had first been reformed over a typical platinumchloride-alumina catalyst to an octane number of 83.3 and the resulting reformate was reformed over on of the catalysts of Example I. In other words, Test No. 2, which employed Catalyst B, an embodiment of the non-noblemetal catalyst of the present invention, as a second catalyst represented a preferred embodiment of the process of the present invention. It can be seen that Test No. 2 provided higher octane numbers for both the C5+mate rial and the heavy ultraformate material. These data demonstrate the superiority of the preferred embodiment of the process of the present invention for the production of high-octane blending material.

EXAMPLE III In this example, Catalyst B, a preferred embodiment of the non-nobel-metal catalyst of the present invention, was tested in a micro-unit as described in Example H. In this case, a higher kinetic average temperature was employed. The results of this test are presented in Table III.

TABLE IIL-TEST DATA Test No 4 4 4 4 Period No--. 1 2 3 4 Catalyst B B B B Pressure, p.s.i.g 300 300 300 300 Avg. temp., F.. 908 913 913 Catalyst wt., gms 20 20 20 Catalyst vol., ce.. 34 34 34 WHSV .31 2. 31 2. 31 LHSV 76 1. 76 1. 76 Hydrogen rate, s.c.f.b... 260 5,280 5, 260 Recovery H 3. 1 88.4 76. 4 05+ research O 1.4 101. 1 101. 1 Heavy ultraformate research oct 4. 1 113. 0 112. 2 Ci-iyield, wt. percent 85. 7 86. 4 85. 9 05+ yield, wt. percent 66. 7 67. 2 67. 1

These data demonstrate the superior ability of the process of the present invention for the production of veryhigh-octane gasoline blending material.

What is claimed is:

1. A process for reforming a petroleum hydrocarbon steam, which process comprises contacting said hydrocarbon stream in a reforming zone under reforming conditions and in the presence of hydrogen with a catalytic composition comprising a hydrogenation component comprising a member selected from the group consisting of a metal of Group VI-A of the Periodic Table of Elements, compounds of a metal of Group VLA, and mixtures thereof supported on a co-catalytic solid support comprising mordenite and a porous refractory inorganic oxide, said mordenite having a silica-to-alumina ratio within the range of about 6 to about 100.

TABLE II.-TEST DATA Test No. 1 1 1 2 2 3 3 3 3 Period No. 1 2 3 1 2 1 2 3 4 Catalyst A A A B B C C C C Pressure, p.s.i a' 300 300 300 300 309 300 309 300 300 Avg. temp., F 897 901 901 904 904 893 894 895 895 Catalyst Wt., gms 20 20 20 20 20 20 20 20 20 Catalyst v01., cc- 32 32 32 34 34 37 37 37 37 WHS 2. 31 2.31 2. 31 2. 31 2. 31 2. 31 2. 31 2. 31 2.31 LHSV 1. 88 l. 88 1. 88 l. 76 1. 76 1. 62 l. 62 1. 62 1. 62 Hydrogen rate, s.c..b 4, 900 4, 730 4, 980 5, 030 5, 5, 070 5, 040 5, 220 5, 000 Recovery Hz), Wt. percen 91. 7 92. 6 92. 8 87. 9 90. 5 86. 4 4. 9 93. 5 94. 7 05+ research octane No., clear 89. 6 89.3 86. 1 100. 3 98. 8 97. 5 95. 9 95. 6 95. 3 Heavy ultraformate research octane No 97. 4 96. 3 101. 7 110.1 105. 4 103. 6 101. 1 103.6 100. 8 04+ yield, wt .percent 97. 4 97. 5 97. 7 91. 4 92. 2 96. 9 97. 2 97. 0 97. 5

05+ yield, wt. percent 2. A process for reforming a petroleum hydrocarbon stream that has been partially reformed, which process comprises contacting said hydrocarbon stream in a reforming zone under reforming conditions and in the presence of hydrogen with a catalytic composition cornprising a hydrogenaton component comprising a member selected from the group consisting of a metal of Group VI-A of the Periodic Table of Elements, compounds of a metal of Group VI-A, and mixtures thereof supported on a co-catalytic solid support comprising mordenite and a porous refractory inorganic oxide, said mordenite having a silica-to-alumina ratio within the range of about 6 to about 100.

3. A process for the reforming of a petroleum hydrocarbon stream, which process comprises contacting said hydrocarbon stream in a rst reforming zone under reforming conditions and in the presence of hydrogen with a catalyst comprising a platinum group metal and a halide on alumina to produce a rst reformate and subsequently contacting said first reformate in a second reforming zone under reforming conditions and in the presence of hydrogen with a second catalytic composition comprising a hydrogenation component comprising a member selected from the group consisting of a metal of Group VI-A of the Periodic Table of Elements, compounds of a metal of Group VI-A, and mixtures thereof supported on a cocatalytic solid support comprising mordenite and a porous refractory inorganic oxide, said mordenite having a silicato-alumina ratio within the range of about 6 to about 100.

4. The process of claim 1 wherein said metal of Group VI-A is molybdenum and is present in an amount within the range of about 2 weight percent to about 20 weight percent, calculated as M003.

S. The process of claim 1 wherein said metal of Group VI-A is molybdenum and is present in an amount within the range of about 2 weight percent to about 20 weight percent, calculated as M003.

6. The process of claim 3 wherein said first reforming zone comprises two or more reactors and said second reforming zone comprises at least one reactor.

7. The process of claim 3 wherein said metal of Group VI-A is molybdenum and is present in an amount within the range of about 2 weight percent to about 20 weight percent, calculated as M003.

8. The process of claim 4 wherein said mordenite of said catalytic composition has been cation-exchanged with a member selected from the group consisting of an alkaline earth metal, a rare earth metal, hydrogen, and a hydrogen precursor to provide an alkali metal content in said mordenite that is less than 1 weight percent, calculated as the metal.

9. The process of claim 4 wherein said refractory inorganic oxide is a catalytically active alumina and said modenite is suspended in and distributed throughout a matrix of said alumina, said mordenite being present in an amount of about 1 weight percent to about 50 weight percent, based on the weight of said support.

10. The process of claim 5 wherein said mordenite of said catalytic composition has been cation-exchanged with a member selected from the group consisting of an alkaline earth metal, a rare earth metal, hydrogen, and a hydrogen precursor to provide an alkali metal content in said mordenite that is less than 1 weight percent, calculated as the metal.

11. The process of claim 5 wherein said refractory inorganic oxide is a catalytically active alumina and said mordenite is suspended in and distributed throughout a matrix of said alumina, said mordenite being present in an amount of about 1 weight percent to about 50 weight percent, based on the weight of said support.

12. The process of claim 7 wherein said mordenite of said second catalytic composition has been cationexchanged with a member selected from the group consisting of an alkaline earth metal, a rare earth metal, hydrogen, and a hydrogen precursor to provide an alkali metal content in said mordenite that is less than 1 weight..

percent, calculated as the metal.

13. The process of claim 7 wherein said refractory inorganic oxide is a catalytically active alumina and said mordenite is suspended in and distributed throughout a matrix of said alumina, said mordenite being present in an amount of about 1 weight percent to about 50 weight percent, based on the weight of said support.

14. The process of claim 7 wherein said rst reforming zone comprises two or more reactors and said second reforming zone comprises at least one reactor.

15. The process of claim 9 wherein said mordenite of said catalytic composition has been cation-exchanged with a member selected from the group consisting of an alkaline earth metal, a rare earth metal, hydrogen, and a hydrogen precursor to provide an alkali metal content in said mordenite that is less than 1 weight percent, calculated as the metal.

16. The process of claim 9 wherein said reforming conditions comprise an average catalyst temperature of about 850 F. to about 1,05'0 F., a pressure of about 50 p.s.i.g. to about 1,000 p.s.i.g., a WHSV of about 0.5 to about 10 weight lunits of hydrocarbon per hour per weight unit of catalyst, and a hydrogen addition trate of about 1,500 s.c.f.b. to about 15,000 s.c.f.b

17. The process of claim 11 wherein said mordenite of said catalytic composition has been cation-exchanged with a member selected from the group consisting of an alkaline earth metal, a rare earth metal, hydrogen, and a hydrogen precursor to provide an alkali metal content in said mordenite that is less than 1 weight percent, calculated as the metal.

18. The process of claim `11 wherein said reforming conditions comprise an average catalyst temperature 0f about 850 F. to about 1,050" F., a pressure of about 50 p.s.i.g. to about 1,000 p.s.i.g., a WHSV of about 0.5 to about 10 weight units of hydrocarbon per hour per weight unit -of catalyst, and a hydrogen addition rate of about 1,500 s.c.f.b. to about 15,000 s.c.f.b.

19. The process of claim 13 wherein said mordenite of said second catalytic composition has been cation-exchanged with a member selected from the group consisting of an alkaline earth metal, a rare earth metal, hydrogen, and a hydrogen precursor to provide an alkali metal content in said mordenite that is less than 1 weight percent, calculated as the metal.

20. The process of claim 13 wherein said reforming conditions comprise an average catalyst temperature of about 850 F. to about l,050 F., a pressure of about 50 p.s.i.g. to about 1,000 p.s.i.g., a WHSV of about 0.5 to about 10 weight units of hydrocarbon per hour per weight unit of catalyst, and a hydrogen addition rate of about 1,500 s.c.f.b. to about 15,000 s.c.f.b.

21. The process of claim 15 wherein said reforming conditions comprise an average catalyst temperature of about 850 F. to about 1,050 F., a pressure of about 50 p.s.i.g. to about 1,000 psig., a WHSV of about 0.5 to about 10 weight units of hydrocarbon per hour per weight unit of catalyst, and a hydrogen addition rate of about 1,500 s.c.f.b. to about 15,000 s.c.f.b.

22. The process of claim 17 wherein said reforming conditions comprise an average catalyst temperature of about 850 F. to about 1,050 F., a pressure of about 50 p.s.i.g. to about 1,000 p.s.i.g., a WHSV of about 0.5 to about 10 weight units of hydrocarbon per hour per weight unit of catalyst, and a hydrogen addition rate of about 1,500 s.c.f.b. to about 15,000 s.c.f.b.

23. The process of claim 19 wherein said refonming conditions comprise an average catalyst temperature of about 850 F. to about 1,050 F., a pressure of about 50 p.s.i.g. to about 1,000 p.s.i.g., a WHSV of about 0.5 to

13 14 about 10 weight units of hydrocarbon per hour per weight 3,549,518 12/ 1970 Mason et a1. 20S-111 unit of catalyst, and a hydrogen addition rate of about 3 705 096 12/1972 Mccaulay et al. 208 65 1,500 s.c.f.b. to about 15,000 s.c.f.b.

3,707,460 12/ 1972 Bertolacim et al 208-65 24. The process of claim 20 wherein said first reform ing zone comprises two or more reactors and said second reforming zone comprises at least one reactor. 5 DELBERT E GANTZ Pnmary Exammer S. L. BERGER, Assistant Examiner References Cited UNITED STATES PATENTS 'U-S- C1X-R 3,033,777 5/1962 Moy et al. 208-79 10 20S-136; 252-455 Z 3,546,102 12/1970 Bertolacini 208--138 UNTTED STATES PATENT OTTTCE QERHMQATE 0F CGRREQTMN March 19 197@ PAT-2m T TTG.

www! im@ l Ralph J Bertolacini et al l rs certified that error appears in the above-Identified patent and that said Letters Patent are harem correced as shown below:

"hydroesulfurization" should be hydrodesulfurizaton Column 6, line 60 ll, 34 "The process of claim l" should be The process of claim 2 "modente" should be mordente efghfeenfh Day of May1976 rr ll, rr 55 RUTH C. MASON Attesling Officer C. MARSHALL DANN Cmnmissimu'r nf Iatvnts and Trademark; 

